Organic compounds

ABSTRACT

The present invention provides novel compounds of the formula:   IN WHICH R1 signifies hydrogen, fluorine or chlorine atom, a carboxylic or sulphonic acid group or an amide or ester thereof, a cyano group or an alkylsulphonyl or arylsulphonyl group, R2 signifies a hydrogen, fluorine or chlorine atom, a cyano group, a phenyl or alkyl radical which may be substituted, a carboxylic or sulphonic acid group or an amide or ester thereof, an alkylsulphonyl or arylsulphonyl group or a benzoxazole group which may be substituted, R3 and R4 independently signify a hydrogen, fluorine or chlorine atom, an alkyl radical of 1 to 6 carbon atoms which may be substituted, a cyano or carboxy group, a carboxylic acid amide or ester group, and R4 may also signify an aryl radical which may be substituted, and A signifies a hydrogen atom or an alkyl or aryl radical which may be substituted or a group of formula II,

United States Patent Aebli et al.

i 1 ORGANIC COMPOUNDS [751 Inventors: Horst Aebli, Basel; Fritz Fleck, Bottmingen, Basel-Land; Horst Schmid, Munchenstein, Basel-Land, all of Switzerland [73] Assignee: Sandoz Ltd., Basle, Switzerland [22] Filed: Dec. 3, 1973 \[21] .Appl. No.: 420,987

Related US. Application Data \[63] Continuation-impart of Ser. No. 255,256, May 22,

71972, abandoned.

[52] U.S. Cl 260/240.1; 252/301.2 W; 252/543;

260/240 C [5 1] int. Cl. C07d 85/98; CO9b 23/l4 [58] Field of Search 260/240.l, 240 C \[56] References Cited UNITED STATES PATENTS 13,759,900 9/1973 Horstmann 260/240 C FOREIGN PATENTS OR APPLICATIONS 12,13L66l Ill/1972 France 2,025,792 5/1970 Germany Primary Examiner-Arthur P. Demers Attorney, Agent, or FirmGerald D. Sharkin; Richard E. Vila; Joseph J. Borovian [57] ABSTRACT The present invention provides novel compounds of the formula:

[ July 29, 1975 3 N l: CH=CH N/ in which R signifies hydrogen, fluorine or chlorine atom, a carboxylic or sulphonic acid group or an amide or ester thereof, a cyano group or an alkylsulphonyl or arylsulphonyl group,

R signifies a hydrogen, fluorine or chlorine atom, a cyano group, a phenyl or alkyl radical which may be substituted, a carboxylic or sulphonic acid group or an amide or ester thereof, an alkylsulphon'yl or arylsulphonyl group or a benzoxazole group which may be substituted,

R and R independently signify a hydrogen, fluorine or chlorine atom, an alkyl radical of l to 6 carbon atoms which may be substituted, a cyano or carboxy group, a carboxylic acid amide or ester group, and R may also signify an aryl radical which may be substituted, and

A signifies a hydrogen atom or an alkyl or aryl radical which may be substituted or a group of formula-ll,

in which B signifies an aryl or heterocyclic radical which may be substituted,

and their water soluble sulphonated derivatives. The compoundsare useful as optical brighteners for various organic materials.

8 .Claims, No Drawings ll 2 ORGANIC COMPOUNDS chlorine atom before or after reduction of the triazole-N-oxide compound to the corresponding This Application is a continuation-in-part of cotriazole compound, or pending application Ser. No. 255,256, filed May 22, b. condensing a compound of formula V, 1972 and now abandoned.

The invention provides novel triazolystryryl triazoles. The invention provides compounds of formula I,

I 3, N a N N 2 N cn= ca N a in Q in which R3-- 2 R, signifies hydrogen, fluorine or chlorine atom, a

carboxylic or sulphonic acid group or an amide or V ester thereof, a cyano group or an alkylsulphonyl or arylsulphonyl group, R R signifies a hydrogen, fluorine or chlorine atom, a I 1 ieyano group, a phenyl or alkyl radical which may be substituted, a carboxylic or sulphonic acid in which R1, R3 R4, A d Z1 and Z2 e as d fi d group or an amide or ester thereof, an alkylsulphoabove, g inyl or arylsulphonyl group or a benzoxazole group with a hydrazinefof formula V] which may be substituted,

R and R independently signify a hydrogen, fluorin i i g VI or chlorine atom, an alkyl radical of 1 to 6 carbon 2 atoms which may be substituted, a cyano or carboxy group, a carboxylic acid amide or ester group, and R may also signify an aryl radical which may i hi h R isvas d fi d above,

be Substituted, and and direct dehyd'rative cyclization of the product to the A signifies a hydrogen atom or an alkyl or aryl radical compound of formula I or oxidative cyclization to the which y be Substituted or a group of formula II, v-triazole-l-oxide compound and reduction of this to B CH CH II the compound of formula I, and in the latter case, when in which B signifies an aryl or heterocyclic radical- Zr signifi s =N H and R signifies hydrogen, with whi h may b b ti d, optional replacement of the R hydrogen substituent by and their water soluble sulphonated derivatives. 21 chlorine atom before or after reduction of the tria- The invention also provides a process for the produc- 40 zole-N-oxide compound to the corresponding triazole tion of compounds of formula I which comprises reactcompound, or ing a hydrazine of formula III, c. reacting a'compound of formula VII,

R\ H N-NH @cH-cn-\ R III i which R,, R and R are as defined above, R 'N with an iso-nitroso compound of formula IV, N. V VII R TR; Z 1

with a compound of formula VIII, in which one of Z and Z signifies an oxygen atom I and the other Z signifies =N-OR, R -N in which R signifies hydrogen or an acyl group, pref- 3 N 2 VIII erably an acetyl group, w N

and A and R are as defined above, and dehydrative cyclization of the reaction product to form the compound of formula I, in which formulae VII and VIII, R to R and A are as or by oxidative cyclization to the v-triazole-loxide defined above, and one of the v and w signifies a compound and reduction of this to the com- ,CHO group or a functional derivatives thereof and pound of formula I and in the latter case when Z, the other signifies a CH -t group, in which 2, signizsignifies =N-OH and R signifies H with opfies hydrogen CN, -COOH, a carboxylic acid ester tional replacement of'the Rrsubstituent by a or amide group in which alkyl is preferably alkyl lower, e.g. with l to phenylethyl, 2-phenoxyethyl, cyclohexyl, 4-methyl- 6 carbon atoms, may be substituted, e.g. by methoxy, cyclohexyl, 4-diphenylyl, naphthyl-l, naphthyl-2, pheethoxy, phenyl or phenoxy, and includes cycloalkyl, nyl, 2-, 3- and 4-methylphenyl, 2-, 3 and 4- e.g. cyclohexyl; aryl is preferably (optionally substichlorophenyl, 2- and 4-methoxyphenyl, 2- and 4- tuted) phenyl; and X is a monovalent anion, e.g. Cl, 10 ethoxyphenyl, 4-fluorophenyl, 2,4- and 2,5-dimethyl- Br, I, CH --OSO C l-l -OSO CH SO phenyl-, 4-n-butylphenyl, 4-tert. butylphenyl, 4-tert.

with cleavage of the substitutent where necessary, amylphenyl and 4-tert. octylphenyl ester groups.

or If R, and/or R are sulphonic acid ester groups, the d. oxidative cyclization of a compound of formula lX, sulphonic acid ester groups corresponding to the afore- R3- N\ N R2 CH=CH N g n Ix A NH R 7 in which R R and R are as defined above, named carboxylic acid ester groups are suitable substit- A' signifies an alkyl or aryl radical which may be uents.

substituted or a group of formula II as defined When a substituent R to R is a carboxylic acid above, amide group or a substituent R or R is a sulphonic R, signifies --CH, COOH or a carboxylic acid 25 acid amide group, the amide is preferably a monoalkamide or ester group, ylamide, dialkylamide, monoand di-(hydroxyalkyl)- to form a compound of formula Ia, amide, alkoxyalkyland alkoxyalkoxyalkylamide,

' R N I 3 R R4 /N O CH=CH ---N A I N Ia amide, N-alkylor N-hydroxyalkyl-N-phenylamide e. oxidative cyclization of a compound of formula X, group, in which alkyl and hydroxyalkyl may contain,

N CH=CH NR A. :N

in which R R R and A are as defined above, and e.g., l to 6 or, preferably, 1 to 4 carbon atoms, alkoxy- R signifies -CN, --COOH or a carboxylic acid alkyl and alkoxyalkoxyalkyl containing preferably 3 to ester or amide, to form a compound of formula 6 and 5 to 8 carbon atoms respectively, aryl and aryllb, oxy may be binuclear or, preferably, mononuclear.

I R Y T N G CH=CH N A \N/ in which R R R' R and A are as defined above. Specific examples are the following amide groups of When a substituent R to R is a carboxylic acid ester carboxylic and sulphonic acids: methyl, ethyl, n-propyl, group it is preferably an alkylestergroup of a carboxiso-propyl, n-butyl, sec. butyl, iso-butyl, n-amyl, n-

ylic acid which has I to 8 carbon atoms in the alkyl radhexyl, iso-amyl, dimethyl, diethyl, di-n-butyl, 2- ical and may be substituted by alkoxy, phenyl or phehydroxyethyl, 2- and 3-hydroxypropyl, 4-hydroxybutyl, noxy radicals or a cycloalkylester or arylester group of di-(Z-hydroxyethyl), di-(2-hydroxypropyl)-, 2- a carboxylic acid, preferably those of the naphthalene, methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3- diphenyl and in'parti'cular the benzene series'Examples methoxypropyl, 4-methoxybutyl, 2-(2-methoxyethoxof suitable carboxylic ester groups are the methyl, 65 y)-ethyl, 2-(2'-ethoxyethoxy)-ethyl, 2-(2'-n-butoxyeethyl, n-propyl, iso-propyl, n-butyl, isobutyl, n-aniyl, thoxy)-ethyl, phenyl, 2-, 3- and 4-methylphenyl, 2-, 3- iso-amyl, n-hexyl, n-octyl, 2-ethylhexyl, 2- and 4chlorophenyl, 2- and 4-methoxyphenyl, 2- and methoxyethyl, Z-ethoxyethyl, 2-n-butoxyethyl, 4-ethoxyphenyl, 4-tert. butylphenyl, 4-n-butylphenyl, 2-(2'-methoxyethoxy)-ethyl, 2-(2'-ethoxyethoxy)- 2,4- and 2,5-dimethylpheny, 4 -diphenylyl, naphthyl-l, ethyl, 2-(2'-n-butoxyethoxy)-ethyl, benzyl, 2- naphthyl-2, N-methyl-N -phe nyl, N-ethyl-N-phenyl,

in which R,, R R R' and A are as defined above, 35 arylamide, aralkyl-, aryloxyalkyland cycloalkyl- N-Z-hydroxyethyl-N-phenyl, cyclohexyl, 4 methylcyclohexyl, benzyl, phenylethyl and phenoxyethyl amide groups.

When R or R signifies an alkylsulphonyl group it may contain, e.g., l to 6 carbon atoms (n-pr0pyl-, isopropyl-, n-butyl-, iso-butyl-, n-amyl-, iso-amylor n-hexyl-sulphonyl and in particular methylsulphonyl and ethysulphonyl). The arylsulphonyl significances of R or R preferably contain aryl radicals of the benzene series such as phenyl-, methylphenyland chlorophenyl-sulphonyl.

When R signifies an optionally substituted alkyl radical this may be branched or unbranched, and preferably contains 1 to 18 carbon atoms especially 1 to 8 carbon atoms and may bear as substituents, e.g., halogen atoms, cyano, hydroxyl, alkoxy, aryl or aryloxy groups, preferably of the benzene series and examples of suitable optionally substituted alkyl radicals are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. butyl, tert. butyl, n-amyl, tert. amyl, iso-amyl, sec. amyl, n-hexyl, n-octyl, 2-ethylhexyl, tert. octyl, n-decyl, ndodecyl, cetyl, stearyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3-methoxypropyl, 4-methoxybutyl, Z-hydroxyethyl, 2- and 3-hydroxypropyl, 2-chloroethyl, 2,2-difluoroethyl, trifluoromethyl, cyanomethyl, cyanethyl, 2-phenoxyethyl, benzyl, Z-phenylethyl and cumyl.

When R signifies an optionally substituted pheny] radical it may be, for example, phenyl, 2-, 3- or 4- methylphenyl, 2-, 3- or 4-chlorophenyl, 2- or 4- rnethoxyphenyl, 2- or 4-ethoxyphenyl, 4-fluorophenyl, 4-ethyl-, 4-iso-propyl-, 4-tert. butyl-, 4-tert. amyl-, 4- tert. octyl-phenyl, 2,4- or 2,5-dimethylphenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-cyanophenyl, 2-, 3- or 4- aminocarbonylphenyl, 2-, 3- or 4-methylaminoor 2-, 3- or 4-dimethylamino-carbonylphenyl, 2-, 3- or 4- ethoxy-, n-butoxy-, benzyloxy-,, cyclohexyloxy-, phenoxyor cresoxy-carbonylphenyl, 3- or 4- sulphophenyl, 3- or 4-amino-, methylaminoor dimethylaminosulphonylphenyl, 3- or 4-methoxy-, nbutoxy-, benzyloxy-, cyclohexyloxy-, phenoxyor cresoxy-sulphonylphenyl.

If R signifies a substituted benzoxazole radical, the substituents may be chosen, for example, from alkyl or alkoxy radicals having 1 to 8 carbon atoms which may themselves be substituted, aryl or aryloxy radicals which may themselves be substituted, chlorine orfluorine atoms, cyano groups, sulphonic acid or sulphonamide groups, alkylsulphonyl or arylsulphonyl groups. Examples of alkyl and alkoxy radicals which may themselves be substituted are methyl to octyl, benzyl, 2- phenoxyethyl, methoxy, ethoxy, n-butoxy, n-octyloxy, cyclohexyl etc. Of the aryl and aryloxy radicals, those of the benzene series are especially preferredzphenyl, methylphenyl, chlorophenyl, fluorophenyl, methoxyphenyl, ethoxyphenyl, cyanophenyl, and the corresponding phenoxy compounds.

If the substituents R to R, are alkyl radicals, these contain only 1 to 6 carbon atoms (methyl to hexyl) and may bear the same substituents as given for R Examples of optionally substituted aryl radicals as significances for R are the binuclear naphthyl-l, naphthyl-Z and diphenyl-4 radicals and in particular the phenyl radicals described above for R When A signifies optionally substituted alkyl or aryl, it may have one of the meanings given above for R R and R,; if it stands for an aryl radical it may in addition correspond to one of the following formulae:

XIV

/N\.' til Q N X m xvI N XVII XVIII in which X, and X independently,,signify a hydrogen,

chlorine or fluorine atom, an alkyl or ,alkoxy group havgroup, or a carboxylic or sulphonic acid amide or ester group, X signifies a. hydrogen atom, a sulphonic acid group or a sulphonic acidamide or ester group, X, signifies a hydrogen, chlorine" or fluorine atom, an aryl group, preferably of the benzene series, anitrile or carboxylic acid group, or a carboxylic acid am'ide or ester group, X signifies a hydrogen, chlorine-or fluorine atom, an alkyl group of l to 6 carbon atoms which may be substituted or an aryl group which may be substituted and which is, preferably of thebenzene-series, y

signifies an oxygenor sulphur atom or an imino group which may be substituted, and m signifies the integer l or 2.

In the above significances X, to X, suitable significances are those set out for R to R, above.

When B in the radical of-formulall) signifies an aryl or hetero ring, it may, for example, .have one of the following formulae: i

in which R is as defined above, and X signifies X, as defined above or an aromatic heterocyclic racical, e.g., a benzoxazole, benzotriazole or naphthotriazole radical, X signifies a hydrogen atom, an alkyl radical with l to 6 carbon atoms which may be substituted or an aryl radical which may be substituted and which is preferably of the benzene series, y signifies an oxygen or sulphur atom, and the pyridine nucleus in formula XXIV may be substituted.

The condensation step of process variant (a) or (b) may be conveniently effected in an inert organic, preferably polar solvent, e.g. in' an aliphatic 'or'aromatic, preferably halogenated or nitrated, hydrocarbon, in an alcohol, ether, glycol, amide, e.g.,f formamide, dimethyl" formamide, dimethyl acetamide, N-methyl pyrrolidone, phosphoric tris-(dimethylamide),.in a nitrile, e.g.acetonitrile, in a sulphoxide or sulphone, e.g. dimethyl sulphoxide-or tetramethylene sulphone, or in a lower alkanecarboxylic acid, e.g. acetic or propionic acid. Suitable reaction temperatures are from 0 to 100C, preferably 20". to C. The reaction is preferably-effected in the presence of an acid,- preferably an organic lower c-arboxylic'acid, e.g. formic, acetic, propionic, butyric, oxalic, tartaric, lactic or citric acid.

Thedehydrative cyclization reaction can be conveniently carried out by heating in the presence of an organic solvent and preferably a tertiary base, together with at least theamount .of a dehydrating agentnecessary for splitting off .1 mol of water.

Examples of'suitabledehydrating agents are the ha,- lides of phosphoric acidsuch as;phosphorus trichloride, oxychloride and pentachloride, and the halides, amides and, preferably, the anhydrides of carboxylic acids, preferably those anhydrides of the lower fatty acids such as acetic, propionic or butyric acid and mixed anhydrides thereof. Among the carboxylic amides, urea as-the diamide of carbonic acid holds a special position. With this dehydrating-agent both the hydrazonoximes and their O -acyl derivatives, preferably their O-acetyl derivatives, can be converted into the corresponding compounds of formula -I. i

The O-acyl derivatives of the hydrazonoximes can also be formed by the reaction of hydrazonoximes with acylating'agents, e.g. acetic anhydride, if necessary in the presence-of a tertiary base such as pyridine, in accordance with the known methods.

An anhydrideof a-lower fatty acid-is an especially preferred dehydrating agent and isv preferablyused in excess. I r

Solvents suitable for the hydrazonoximes and their O-acyl derivatives are those inert solvents which do not affect the dehydrating agents; examples are aromatic and chlorinated hydrocarbons, ethers, ketones, acidamides, sulphoxides and sulphones. Especially valuable solvents are acid amides, sulphoxides and sulphones, e.g. dimethyl formamide, diethyl formamide, dimethyl acetamide, N-methylpyrrolidone, dimethyl sulphoxide, dibutyl sulphoxide, tetramethylene sulphone (sulpholan) and phosphoric tris-(timethylamide).

Depending .on the solubility of the hydrazonoxime, the solvent is usually employed in an amount which. is equal to'or several times greater than the weight of the hydrazonoxime'.

The tertiary base maybe used in stoichiometric or catalytic amounts. Of the tertiary bases whose presence promotes the reaction, special mention may be made of diethylaminobenzene, dimethylaminobenzene, quinoline, pyridine, alkylpyridines and technical mixtures of pyridine bases. i i

The favourable temperatue range for the cyclization I reaction giving the triazole is 20 to.200C, in particular .PCl'fltLlI'E of to 210C, preferably to l75C. It is not necessary to dry the hydrazonoxime prior to cycli-zation. The moist hydrazonoxime can be added, for

example, to a urea melt. During the heating-up period the water evaporates and cyclization takes place. It is preferred to employ two to twenty times, especially three to fifteen times the amount of urea in relation to the dry amount of the hydrazonoxirne. A combination of urea and a lower fatty acid, e.g. acetic acid, is particularly advantageous.

The oxidative cyclization may be effected by the action of a wide variety of oxidizing agents; for this reaction the useof oxidation-stable solvents is advisable. Suitable oxidizing agents include bichromate and hydrogen peroxide in acid, for example acetic acid solution, and potassium ferricyanide in basic solvents such as pyridine and pyridine-water mixtures. A generally cmployable and preferred process consists in oxidation with a copper (ll) salt such as copper (I1) sulphate, chloride or acetate in a pyridine-water mixture. The cupric salts can be employed in stoichiometric amounts or in excess of or below the stoichiometric amount. The imonovalent copper formed in the reaction can be continuously converted into the divalent stage during the reaction by blowing in air or oxygen.

The reduction of the triazole oxides to the final compounds is carried out in conventional manner, preferably using nascent hydrogen from a base metal and an acid, especially zinc dust in acetic acid, in an acetic acid-water mixture or in a mixture of acetic acid and an linertorganic solvent, preferably chlorobenzene. The reaction can be conveniently carried out at temperatures from room temperatureto about 150C, the preferred range being 60 to 130C. The reduction can also be carried out at a lower temperature, if necessary with a small addition of an inorganic acid, e.g. hydrochloric acid, for acceleration. The salts of reducing acids of sulphur or phosphorus can also be used for rerluction.

Simultaneously with reduction of the oxide to the v triazole ring, treatment of the triazole oxide with hydrogen chloride leads to the introduction of a chlorine atom in the -position of this ring adjacent to the N- oxide grouping, when R or R stand for hydrogen. This reaction is preferably conducted with gaseous hydrogen chloride, which is introduced into a dispersion of the N-triazole oxide in'a mixture of water and a watersoluble organic solvent, preferably an alcohol or ether e.g. ethanol, propanol, butanol, methyl glycol, ethyl glycol, ethylene glycol, diethylene glycol or dioxan, at the reflux temperature of the reaction mixture. These chlorine-containing compounds can also be formed by reacting the N-triazole oxide with a chlorinating agent, e.g. sulphuryl chloride, thionyl chloride or phosphoryl chloride, in a solvent inert to halogenation, with subsequent reduction with nascent hydrogen to the 5-chloro- N-triazole compound as described above.

ln process variant (c) the reaction of a compound of formula V1] with a compound of formula VIII, in which the aldehyde group is present as such or in the form of a derivative, e.g. the oxime, hydrazone, azine or anile, is preferably carried out in the presence of a suitable condensing agent or catalyst, e.g. boric acid, zinc chloride, arylsulphonic acid, an alkali or alkaline-earth metal salt of an arylsulphonamide, acetic anhydride, an alkali metal acetate, piperidine, an alkali or alkalinecarth metal hydroxide or an alkali or alkaline-earth metal alcoholate. Suitable temperatures are from 0 to 200C, preferably from to 160C. If t, stands for hyldrogen, the progress of the reaction is assisted if the adjacent benzene nucleus bears a negative substituent, e.g., CN, -COOH, -SO l-l or an optionally substituted ester or amide group of a carboxylic or sulphonic acid. If a radical t, other than hydrogen is present in the reaction product, it is removed by suitable means, or more exactly is replaced by a hydrogen atom. With a reaction product is which t, is a COOH group, this removal can be effected, for example, by heating to about 200C in a solvent of high boiling point, e.g. a tertiary amine such as quinoline; if t is a cyano, carboxylic amide or ester group the step is carried out with prior acid or alkaline saponification of this group to the carboxy group. If, however, t in the starting product is a phosphorus-containing ester group, this group is replaced by a hydrogen atom during the course of the reaction of the compounds of formulae V1] and VIII. I

The reaction can be carried out effectively by fusing the reactants, though it is preferred to use an inert solvent, e.g. an aliphatic or aromatic, preferably halogenated hydrocarbon, one of the alcohols, ethers or glycols, an amide such as formamide, dimethyl formamide or acetamide, N-methylpyrrolidone, phosphoric tris- (dimethylamide), acetonitrile, dimethyl sulphoxide, tetramethylene sulphone.

In the above process variants (a), (b) and (c) the reactants are preferably used in approximately equimolar proportions.

The oxidative cyclization of compounds of formulae IX or X in process variants (d) and (e) can be conveniently carried out in the presence of an oxidationstable organic solvent, such as: hydrocarbons, including halogenated or nitrated hydrocarbons, e.g. benzene, toluene, chlorobenzene, ortho-dichlorobenzene, bromobenzene, nitrobenzene, l-2-dichlorethane, l,l,2,2-tetrachlorethane; amides, e.g. dimethyl formamide, dimethyl acetamide, phosphoric tris- (dimethylamide); sulphones, e.g. tetramethylene sulphone; ethers, eig. methoxybenzene, ethoxybenzene, dioxan, 1,2-dimethoxyand 1,2-diethoxy-ethane; and tertiary amines, e.g. dimethylaminoand diethylaminobenzene, triethylamine, tri-(n-butyl)-amine, pyridine, picoline, q'uinoline and mixtures of pyridine bases.

Suitable oxidizing agents include alkali metal hypohalogenites, preferably sodium hypochlorite or hypobromite; inorganic and organic copper (11) compounds such as copper (ll) chloride, sulphate, acetate, carbonate and naphthenate, which are employed preferably in the presence of nitrogenous bases such as ammonia, amines such as trimethylamine, ethanolamine, diethanolamine, triethanolamine and pyridine; and air or oxygen in the presence of a copper (11) compound, of which the latter can be employed in catalytic to stoichiometric amounts or in excess.

The oxidative cyclization reaction can be conve niently effected at temperatures ranging from 0 to 150C, the preferred ranges beingfrom room temperature to 40C when the oxidizing agent is one of the alkali hypohalogenites and to C for oxidization with a copper compound alone or with oxygen or air in the presence of a copper (11) compound in an amount of, e.g., up to 10 of the stoichiometric amount.

The compounds of formula 1 may be isolated by the known methods, e.g. by cooling, dilution with a suitable agent, partial or complete evaporation of the solvent or solvents, steam distillation etc., followed by filtration,

washing if necessary, and drying and purified in conventional manner.

It will be appreciated that the compounds of formula I may be converted into further compounds by substitution and/or further cyclization. Thus, for example, in a compound of formula I in which one of the substituents is, or has a substituent, an acid group, such group may be converted into an ester or amide group. Also, for example, a compound of formula I in which A and/or R signifies an amide of an o-hydroxyarylamine with a carboxylic or phenylcarboxylic acid radical, may be subjected to dehydrative cyclization to form a compound of formula I in which A and/or R is a naphthoxazolyl, benzoxazolyl, naphthoxalylphenyl or benzoxazolylphenyl radical.

To convert water-insoluble triazolyl styryl triazoles of formula I into the corresponding water-soluble sulphonated compounds they can be treated with sulphonating agents, e.g. concentrated sulphuric acid of 90 to 100 strength, weak oleum with an S content of up to about 30 chlorosulphonic acid or gaseous sulphur trioxide. The temperature may range from 0 to about 100 C, or preferably from 20 to 5060C, and sulphonation is continued until the number of sulphonic acid groups, e.g. 1 to 3, required to impart solubility in water has been introduced. If chlorosulphonic acid or gaseous sulphur trioxide is used, sulphonation proceeds satisfactorily in an inert solvent such as sulphuric acid, ortho-dichlorobenzene or nitrobenzene, while if concentrated sulphuric acid or oleum is chosen the sulphonating agent itself may serve as solvent. The compounds of formula VII in which v signifies CH0 and R, signifies SO H can be produced from the 4,4-bis- [4 -phenyl-v-triazolyl-2 ]-stilbene-2,2 -disulphonic acids disclosed in British Patent 1,108,416 by cleavage with potassium permangate in aqueous-alkaline medium (see German Patent 115,410).

The compounds of formula VIII in which w stands for -CH --PO=(Oalkyl) can be derived from the corresponding compounds bearing a CH Cl group by reaction with a trialkyl phosphite.

The starting compounds of formula IX, as defined above, can be produced, for example, by coupling diazo compounds from amines of formula XXVI,

XXVI

with enamines of formula XXVI] A C-NH XXVII in which R, and A are as defined above, or with their tautomeric ketimides, e.g. with ,B-aminocrotonic nitrile, ester or amides or with B-aminocinnamic nitrile, ester or amides. In an analogous manner, compounds of formula X as defined above can be obtained by coupling diazo compounds from amines of formula XXVIII,

XXVIII in which R is as defined above, with enamines of formula XXIX,

in which R R R and A are as defined above, or with their tautomeric ketimides.

In so far as the production of the starting materials is not described, the compounds are known or may be prepared by known processes, or in a manner analogous to known processes. The new triazolylstyryl triazoles of formula I possess properties suitable for the optical brightening of a wide variety of organic materials and polymeric materials.

A preferred group of optical brighteners according to this invention are those of formula Ic,

in which T signifies a hydrogen atom or an alkyl radical of l to 4 carbon atoms.

An especially preferred group of optical brighteners according to the invention are of formula Id,

in which R signifies the nitrile group or the sulphonic acid group (which may be present as an alkali metal salt, preferably the sodium salt), R signifies a hydrogen atom or the nitrile group, R signifies a hydrogen or chlorine atom or the methyl group, R signifies a hydrogen or chlorine atom or the methyl group, A signifies the phenyl radical or a radical of formula in which T signifies a hydrogen atom or the methyl or tertiary butyl radical, and

T signifies a hydrogen atom or the methyl or nitrile group.

By "organic materials are understood natural fibres, e.g. cellulose (paper and cotton) and natural polyamides (wool, silk), and by polymeric materials the synthetic and semi-synthetic polymers, e.g. polyesters, polyamides, polyurethanes, polyolefins and optionally, modified polyolefins, polypropylene including polypropylene modified by the introduction of basic groups), polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile and modified polyacrylonitrile and acrylonitrile, polystyrene, cellulose (2 1/2) acetate and cellulose triacetate.

The compounds of formula I can be applied to the substrate desired to be brightened by any of the standard exhaust, padding or printing methods, either in the form of solutions in water or an organic solvent or as aqueous dispersions. But they can also be advantageous as brightener additives in spinning solutions and melts, in plastics moulding materials, and in the monomers or prepolymers for the synthesis of polymers. For this latter purpose the water-insoluble triazolylstyryl triazoles of formula I are preferable.

Depending on the method of application, the disclosed compounds are employed in amounts of 0.001 to 0.5 8L or preferably 0.01 to 0.2 in relation to the weight of the material. They are suitable for use alone or in combination with other optical brighteners, and may be applied in the presence of surface-active agents, for instance detergents, carriers, and chemical bleaching agents. An effective method of brightening heat-stable synthetic fibres, notably polyester fibres, in fabric form is to pad the selected compound of formula I on the fabric from an aqueous medium containing a surface-active agent and to treat the fabric in dry heat, e.g. at l50240C or preferably l80-220C, in accordance with the thermosol process.

The disclosed brighteners have a distinct reddish violet to blue fluorescence shade, a high saturation limit, good sublimation fastness and good light fastness. The water-soluble compounds containing sulphonic acid groups can be incorporated in powder, paste or liquid detergents in amounts of, eg 0001 to 0.5% relative to the solid content of the detergent. This group of brighteners may also be used for the optical brightening of cellulosic fibres (cotton, linen, hemp, paper, rayon) and polyamide fibers (wool, silk, hair fibres, polyamide 6, 66, 610, ll etc.) by the exhaust technique and, in particular, for the optical brightening of nonwovens and carpets by discontinuous or continuous padding processes. In the following Examples the parts and percentages are by weight and the temperatures in degrees centigrade. The melting points are uncorrected.

EXAMPLE 1 21 Parts of 4-hydraiino-2-cyano-B-(2'- phenylosotriazolyl)-styrene are dissolved in 67 parts of dimethyl formamide at room temperature. 43 Parts of 50% acetic acid are added, then in the course of 1 hour 19.7 parts of 1-p-benzoxyzolyl-phenyl-l-hydroxyiminoacetone are gradually added with thorough stirring. The reaction mixture is stirred further for 3 hours at room temperature and 2 hours at 60, cooled slowly to 3 and filtered with suction to separate the yellowbrown precipitate. This is washed with 64 parts of methanol cooled mice and dried at 60 with vacuum to give 28 parts of the hydrazonoxime. Without further purification the hydrazonoxime is dissolved in 58 parts of dimethyl formamide, followed with const'ant' stirring by 54 parts of pyridine and then by 27.5 parts of acetic anhydride. In the space of 2 hours the temperature is increased to and in a further hour to about 135 (reflux). The batch is cooled slowly to' 5, the yellow precipitate filtered with suction, washed with ice-cold methanol and dried at 80 with vacuum. After recrystallization several times from chlorobenzene, pale yellow crystals are obtained with melting point 255-257 which fluoresce with a red-violet shade in chlorobenzene solution and agree with the formula (Amax. in CHCl 365 nm). I

The 4-hydrazino-2-cyano-B-(2'-phenylosotriazolyl)- styrene used as starting product can be produced as follows.

57.4 Parts of 4-amino-2-cyano-B-(2'- phenylosotriazolyl)-styrene (see Belgian Patent 722,920) are suspended in 415 parts of 2- methoxyethanol and the suspension added to a thoroughly stirred mixture of parts of concentrated hydrochloric acid, 165 parts of ice and l 15 parts of water. After stirring for 3 hours at 10 the beige suspension is cooled to 0 and diazotized by the addition of a solution of 13.8 parts of sodium nitrite in 30 parts of water. The reaction mixture is stirred for a further 2 hours at 0-5 after which the excess nitrous acid is decomposed with urea. The diazonium salt mixture is stirred well into a mixture of parts of. tin (ll) chloride and 225 parts of concentrated hydrochloric acid, and cooled to 10. Stirring is-continued for 4 hours at 5 to 0. The precipitate is filtered off with suction, treated on the filter with 205 parts of concentrated ammonia, washed well with water after the treatmennpurified by dissolving in 2-methoxyethanol and precipitating with water, and finally vacuum dried at 70. A yellow compound of formula 2 \N cn=cn XXXIII melting point l40-144, is obtained in. a yield of 51 parts.

H ll-NH EXAMPLE 2 I parts of 4-hydrazino-2-cyano-B-(2- phenylosotriazolyl)-styrene are condensed with 22.7 parts i of l-p-(5-tert.butyl-benzoxazolyl)phenylhydroxy-iminoacetone as described in Example l. Without further purification, the resulting hydrazonoxime compound is cyclized by the method there given. The crude product, which is obtained in a yield of 19 parts, is recrystallized several times from glacial acetic acid or from chlorobenzene with the aid of bleaching earth and the addition of a small amount of zinc dust, on which almost colorless crystals with melting point 224-226 are obtained. They dissolve readily in nearly all organic solvents, show red-violet fluorescence and have the formula are suspended in 40 parts of dimethyl formamide, with the subsequent addition of 60 parts of acetic anhydride and 60 parts of pyridine. The suspension is held for 2 hours at 80, for 2 hours at 100 and then for 30 minutes at boiling temperature. When it has cooled the yellow-brown precipitate is filtered, washed with ice-cold methanol and dried. The product has the formula,

' \i CH= HOOC Q N/ I CN E" N onn and can be reacted by one of the two following methods (a) or (b).

a. 15 Parts of the p-carboxyphenyl triazole compound, 6 parts of l-hydroxy-2-aminobenzene and 8 parts of boric acid are ground fine and mixed with 5 parts of ethylene glycol. The mixture is heated under a nitrogen gas current with simultaneous distillation of the water of reaction, the reaction being continued for 1 hour at 140 and 3 hours at 200. After this time the mixture is cooled slowly with addition of 10 parts of ethylene glycol at 140 and 10 parts of methanol at 60. When 5 is reached the precipitate is filtered, washed with cold'methanol and crystallized from chlorobenzene. Pale yellow crystals of melting point 254-257 areobtained, which fluoresce with a red violet'shade in chlorobenzene solution ()tmax. in CHCl 365 nm). This compound corresponds to formula le.

b. 12 Parts of the para-carboxyphenyl triazole compound are stirred into 138 parts of chlorobenzene, 55 parts of the chlorobenzene are distilled (azeotropic drying) and the mixture then allowed to cool in the absence of moisture. One part of dry dimethyl formamide is added, followed by 4 parts of thionyl chloride, and the reaction with the chloride carriedout by holding the mixture for 15-30 minutes at about 130. On cooling the acid chloride formed is filtered, washed with benzene and vacuum dried. 10 Parts of the crude acid chloride are suspende d in l 10 parts'of dry chlorobenzene at room temperature, 3.5 parts of l-amino-2- hydroxybenzene'and 1.75 parts of pyridine are added, the "mixture raised to the refluxing temperature (l30l35 under a nitrogen gas current with [good stirring, and held at this temperature for 6 hoursJOn cooling the precipitated acid amide is filtered, washed with methanol and vacuum dried. i v

1 1 Parts of the acid amide are mixed with 10 times the amount of 1,2,4-trichlorbenzene with the addition of 5 boric acid relative to the amide. The mixture is raised to the boiling temperature (2l0-2l 5) under a nitrogen gas current and held at this temperature, with distillation of the water of reaction and some trichlorobenzene, for 4-15 hours to the end-point of the reaction. After cooling to 50, 100 parts of methanol are added toprecipitate the benzoxazole compound, which is filtered and purified by recrystallization as given in a). The same product as in a) is obtained in a yield of 8.7

parts. g

EXAMPLE 4 10 Parts the hydrazonoxime of formula v CH 3 t Erwin tert c H 4 N I 9 v H 0C N CH N N cu=cn- N xxxvrr are mixed with 20 parts of dimethyl acetamide, 20 parts of acetic anhydride and 20 parts of a technical mixture of pyridine bases. The mixture is raised in 2 hours to in 3 hours to and in l hour to boiling temperature. As itcools the triazole compound settles out as a finezprecipitate which is isolated in the normal way. The'crude product is added to ortho-dichlorobenzene together with a catalytic "amount of boric' acid (about 5 %relative to the-hydrazon0xime) and cyclized at boiling temperature to the azole-compound as in Example 3b). The compound ()tmax; 365 nm, e: 8.4 l0) corresponds to formula] f). Ring closure to the triazole can be accomplished with equal success using dimethyl sulphoxide. tetramethylene sulphone. or phosphoric tris-(dimethylamide) as solvent in place of dimethyl acetamide.

if the hydrazonoxime used in this Example is replaced by a hydroazonoxime in which the 2- hydroxyphenylamino radical to the left is substituted by one or more lower alkyl and/or alkoxy groups or a phenyl group, compounds with very similar properties are obtained. All these compounds exhibit intense violet fluorescence in solution, and owing to their good fastness properties are suitable for the optical brightening of synthetic polymer materials.

The hydrazonoxime required as starting material can be formed,for example, by coupling a diazonium salt of 4-amino-2-cyano-B-(2-phenylosotriazolyl-)-styrene with a corresponding acetoacetylaminobenzene with subsequent oxime formation.

EXAMPLE 5 20 Parts of the hydrazonoxime of formula 7 carried out at 40-50 with splitting off of the sulphonic tions so that the internal temperature does not increase acid group. These compounds are in the form of pale yellow powders and are particularly suitable for application in polyamide and polyester spinning melts to brighten the spun filament. Alternatively they can be obtained by the route described in Example 1.

EXAMPLE 6 51 Parts of the dry oxime hydrazone of formula F N OH \N @.=.N.NH -N 0 Na. 3 are added in portions to 200 parts of melted urea at about 130 with thorough stirring. The reaction mix-' ture is stirred further for 4 hours at 160. When the evolution of gas has ceased it is allowed to cool to 130,

XXXVIII at which temperature a mixture of 27 parts of concentrated sodium hydroxide solution, 20 parts of common salt and 20 parts of water is added. The precipitate is filtered with suction while hot and precipitated several times from aqueous dimethyl formamide with the aid of decolourizing carbon. Almost colourless crystals are obtained which dissolve readily in aqueous solvents and hot water to give solutions showing intense violet fluorescence. This compound has the formula SO Na The oxime hydrazone of formula (XL) canbe produced as follows; 35.7 Parts of 4-hydrazino-[3-(2' coupled with 2.5 parts of l-amino-3-methoxy-4- methylbenzene to the ortho-aminoazo compound. This is oxidatively cyclized in pyridine at about 70 in the presence of 1.2 parts of crystallized copper acetate by the introduction of air. The product has the formula It is purified by recrystallization from chlorobenzene using decolourizing carbon and a trace of zinc dust.

If 2.65 parts of Z-naphthylamine are employed as coupling component in this Example in place of lamino-3-methoxy-4-methyl-benzene and the same procedure followed, an equally effective product is obtained. If 4.5 parts of Z-naphIhylamine-l-sulphonic acid are used as coupling component, coupling is best phenylosotriazolyl)-styrene-2-sulphonic acid (produced in analogy with the method given in Example 1 for the starting product there used) are suspended in [000 parts of water'and sufficient 3O sodium hydroxide solution is added to adjust the pH to 6.5. A solution of 15 parts of oximinoacetophenone in 48 parts of methanol is allowed to flow in and the mixture stirred for 1 hour at pH 5-6 and 70. When no further hydrazino compound is indicated the methanol is distilled from the mixture at reduced pressure, a concentrated sodium chloride solution added and the precipitate filtered with suction. After vacuum drying at 40 the compound can be reacted further without purification.

It contains approximately 80 of the desired oxime ()1 hydrazone. I

CH=CH 'N EXAMPLE 7 20" Parts of 4-hydrazino-2-c yano-B-(2- 5 phenylosotriazolyl)-styrene are added to 48 parts of di- N\ methyl formamide with heating to 60, on which it goes I into solution almost completely. After cooling to 20 CH=CH with vigorous stirring, 42 parts of 50 acetic acid are Ik added, followed in the course of l hour by portions of isonitrosobenzalacetone totalling 13 parts. The mixture is held for a further 3 hours at 25 with thorough max in chloroform; 370 nm) stirring and then for 2 hours, at 60 until no further hydrazine is indicated. It is cooled slowly, first to room EXAMPLE 9 temperature and then in an ice bath to 03. The yel- 15 28 parts of the triazo|e N oxide of formula low precipitate is filtered with suction and washed with ice-cold methanol to give a yellow-brown hydrazonox- O ime, melting point 195220, which without further l purification is suspended in 14 parts of dimethyl form- I N amide at room temperature, with the consecutive addi- 0 CH=CH N II II tion of 12 parts of pyridine and 5.5 parts of acetic anhydride. The temperature is raised to 80 in 2 hours and in the following 2 hours to 100. A dark brown solution is formed which is boiled for a further 30 minutes with N \l@ reflux. It is cooled slowly to O-5 and the precipitate 25 CH=CH-= filtered with suction, washed with ice-cold methanol XLV and crystallized from chlorobenzene with the aid of bleaching earth. The compound of formula i melting point 233-235, \VhlCh can be produced In 3 analogy with the procedure of Examples 7 or 8, are em- CH: 1 IN -CH=CI-[ ployed for reaction in otherwise complete accordance N N with Example 8, and lemon crystals, melting point l94-l95, are obtained which exhibit violet fluores- I] cence in chlorobenzene solution and agree with foris obtained in the form of pale yellow crystals, melting mula point 203205, which fluoresce with a violet shade in chlorobenzene solution ()tmax. 365 nm).

I EXAMPLE 8 3 CH=CH =N/N 50 Parts of the hydrazonoxime of Example 7 are dis- 40 solved in 300 parts of pyridine with heating to 90. In minutes a solution of 40 parts of copper sulphate pentahydrate, 90 parts ofwater and parts of pyridine is added dropwise with stirring. The reaction mix- CH-CH ture is held for 2 /2 hours at 90-l00, then 300 parts 45 of pyridine-water mixture are distilled with vacuum, I1 the mixture cooled and the precipitate filtered with suction. It is washed with 1000 parts of dioxan and then withwater until the wash water is colourless, and dried in o o o m: 373 nm) at 60. with vacuum. The yellow-brown trlazole-N-oxide EXAMPLE 10 formed melts at 229 233 and corresponds to the formula 4.5 Parts of the phosphonic ester of formula 27 Parts of this triazole-N-oxide are dissolved in 300 parts of dioxan and 2 parts of water at 85. For 5 hours a powerful current of hydrogen chloride gas is directed N I- into the well stirred solution. After a short time it be- CH=CH gins to fluoresce and lemon crystals settle out. On completion of the reaction time the batch is cooled and the product filtered with suction. Crystallization from chlo- 5 o robenzene with the aid of bleaching earth results in n C H lemon crystals with melting point 202204, which flu- CH 2 5 oresce with a violet shade in chlorobenzene solution 2 and have the formula 2 5 XLVII -to.l. The product is isolated by filtration with suction and vacuum dried at 60. Almost white, needle-shaped crystals are obtained in a yield of 11 parts, which following recrystallization from chlorobenzene melt at 23 3-23 5. They are of formula 3.1 Parts of the crystalline product are suspended in 100 parts of dry carbon tetrachloride, set for reaction NC N CH=CH-==N) CH=CH u my u r i (Amax. in chloroform: 367 nm) EXAMPLE 1r 30 Parts of the phosphonic ester of formula (XLVll) along with 13.5 parts of 2-(4-cyanophenyl)-4-formyl- 1,2,3-triazole are dissolved in 200 parts of distilled dimethyl formamide. A solution of 3.7 partsof sodium methylate in 8 parts of methanol is added at 30 and the batch stirred for 1 hour at this temperature, after which 100 parts of methanol are added, the mixture cooled to 10 and the product isolated by filtration with suction. On recrystallization from ortho-dichlorobenzene, pale yellow crystals with melting point 3l7-3l9 are obtained, which fluoresce with a blue-violet shade in chlorobenzene solution and corresponds to the formula with 2 parts of N-bromosuccinimide and 0.l part of benzoyl peroxide and reacted for 8 hours with reflux. The precipitated succinimide'is filtered off, the filtrate condensed by evaporation and the residue recrystallized from toluene. 4 Parts of the resulting bromdmethyl compound, melting point l l4-l 18, are converted with triethyl phosphite into the phosphonic diethyl ester of formula (XLVII), crude melting point 2l0-220, following the known method of Michaelis- Arbusov (A. Michaelis, Liebigs Ann. Chem. 326, (1903), 129). i v In table 1 below further optical 'brighteners according to this invention are specified which have the general formula 3135:\ 'f\ R H N- crucnand can be produced analogy with the operating procedures of Examples 1 or 7.

Table 1 Example Fluorescence shade 15 m u m in chlorobenzene 12 CN CH 5 iso-OctylbenzoxazolylQ red-violet 13 do. do. do. S-Methylbenzoxazolyl-Z do.

14 do. do. do. 5-Ethylbenzoxazolyl2 do.

l5 do. do. do. S-Phenylbcnzoxazolyl-Z do.

16 do. do. do. 5-tert.Amylbenzoxazolyl-2 do.

17 do. do. do. 5-Chlorobenzoxazolyl-2 do.

[8 do. do. do. 6Chlorobcnzoxazolyl-2 do.

19 do. do. do. 6-Phcnylbcnzoxazolyl-2 do.

20 do. do. do. 5-Cyanobenzoxazolyl-2 violet 21 do. do. do. 6-Cyanobenzoxazolyl-2 do.

Table l -Continued Example Fluorescence shade u; 1: 14 R15 in chlorobenzene 22 do. do. do. do

23 H H CH=CH Diphenylyl-4- blue-violet f 24 CN H do. I I blue 25 C N H do. I I do.

26 CN H do. blue-violet 27 CN H do. blue 28 H H do. do. blue-violet The following Table2 gives details of a further number of compounds which have the general formula be ra eu en- SO Na Following the procedure of Example l or 7 and employing appropriate starting materials in approximately equiyalent-amounts, the compounds in the following Table-III, and which agree with the formula may be produced.

Table 2 Example N0. R R Hydroxyimino ketone 29 phenyl CH hydroxyimino propio- V phenone '30 4-methylphenyl para-methyl hydroxyiminoacetophenone 3 l 4-chlorophenyl para-chloro hydroxyiminoacetophenone 32 4-methoxyphenyl para-methoxy hydroxyimino acetophenone 3 3 3-cyanophenyl CH l-( 3 -cyanphenyl l -hydroxyimino acetone 4 34 4-diphenylyl H para-phenyl hydroxyimino acetophenone 35 phenyl phenyl benzile monoxime 36 ethyl CH hydroxyimino diethyl ketone 37 phenyl C H hydroxyimino butyrophenone 38 4-carboxyphenyl CH l-(4'-carboxyphenyl)- l hydroxyimino acetone 39 so Na H4- CH sulphenyl)-lhydroxyimino acetone 40 CH l-( 3 '-sulphophenyl l SO Na hydroxyimino acetone 41 4-methoxyphenyl Cl para-methoxy hydroxyimino ucetophenonc TABLE II] Example No. R, R,; R R,, T, T Fluorescence shade Bluish in cellosolve/ l-2 SO H 4Cl C] H H H water 43 --SO NH 4CH,, CH OH Cl H H Violet in chlorobenzene Bluish violet in 44 CONH 4-CN CH;, CH 4C N 6CN chlorobenzene 45 CN 4-CONH CH Cl CH OCH H o. 46 C N H CH- CH H H Violet in chlorobenzene OCOCH Red-violet in chloro- 47 CN H CH CH H H benzene 48 CN CIH H CH 5C N H Violet in chlorobenzene C C H Application Example A A mixture of 10 parts of the compound of formula I f, 22 parts of a highly sulphonated castor oil, 8 parts of sodium dioctylphenylpolyglycol etheroxyacetate containing 40 ethenoxy groups in the molecule, and 80 parts of water is prepared for comminution in a suitable machine, for example a sand mill. Grinding is continued until a particle size distribution of zero 0.5-2 microns is reached for the major proportion of the dispersion.

A fabric of polyester fibre, e.g. polyethylene terephthalate, is padded with a solution of 20 parts of the ground dispersion in l000 parts of water at room temperature and with an expression giving an increase of 80 on the dry weight. After intermediate drying for 30 minutes at 60 the brightener is thermofixed for 1 minute at 220. A pronounced white effect is obtained on the fabric. This brightening method is of course equally effective with polyester fibres of the type synthesized from terephthalic acid and l,4-,dimethylol cyclohexane. If a dispersion whose active substance corresponds to the product of Example 16 is used in place of the one described above, comparable white effects are obtained.

Application Example B In the tank of a melt spinning machine 200 parts of polyethylene terephthalate are melted at 280 in a nitrogen atmosphere, and 0.4 parts of the brightener compound of formula I e stirred into the melt. When it has homogeneously dissolved 4 parts of titanium dioxide are added as delustrant, with continued stirring for homogeneous distribution. The melt is spun through a nozzle, the newly formed filament cooled by a water jet and then cold drawn and wound on bobbins.

Textiles made of this spun filament are very much whiter in appearance than comparable products of filament spun without a brightener additive. In place of the aforestated compound, one of the compounds disclosed in Examples 13 or 14 can be chosen, with which similar-white effects are obtained.

4 Application Example C In a stainless steel autoclave fitted with a stirrer and a descending cooler, a batch of 1000 parts of dimethyl terephthalate, 665 parts of ethylene glycol, 0.55 parts of manganese acetate, 018 parts of antimony trioxide and 0.6 parts of the compound of formula I e is heated for reaction. Splitting off of the methanol begins at about 160 and takes 2 /2 hours to complete. Subsequently 4 partsv of titanium dioxide and 0.3 parts of phosphoric acid are metered into the melt, the pressure in the autoclave reduced to below 1 mm and the temperature held at 290 until the desired degree of polymerization is reached. The polyester thus formed is spun in filament form by the normal method at 2-5 atmospheres excess pressure (inert gas). The filament exhibits a high degree of whiteness which is very resistant to light and washing.

Application Example D I A batch of polyamide 6 (poly-e-caprolac tarn) granules is powdered in a mixer with 0.01-0.05. of its weight of the compound of Example 3 or 13. lt is transferred to a melt spinning machine, where it is melted under nitrogen for 30 minutes at about 300", stirred for 15 minutes at this temperature, raised to the spinning temperature, 285, and spun as monofilament at 3-5- atmospheres excess pressure (nitrogen). ln daylight the filaments fluoresce with a violet shade. They appear much whiter and brighter than filament with no incorporated brightener. If in place of polyamide, polyester or polypropylene is set with one of the stated brighteners and spun at290 or 260 respectively, monofilaments showing a higher degree of whiteness than unbrightened filament are obtained.

Application Example E Application Example F In a mixer, parts of polypropylene granules are powdered with 0.01 part of compound I h. The material is worked up on a three-roll mill at l44l 20 and then either extrusion moulded as panels or regranulated and injection moulded. The moulded products exhibit greatly: improved whiteness over unbrightened articles. The polypropylene can be replaced by low-density or high-density polyethylene, another polyolefin, polystyrene or cellulose acetate,

27 Application Example G A solution of 0.005 parts of the compound of formula Ij in a plasticizer is blended with 100 parts of moulding material consisting of 65 parts of polyvinyl chloride and 35 parts of a plasticizer, e.g. dioctyl phthalate, and containing 2 relative to the polymer content, of a stabilizer. The material is worked on a roll mill for minutes at l50-l60 and extruded as film. If opaque film is desired, 2.5 titanium dioxide is incorporated in the 28 Application Example L A fabric of polyamide 66 fibre is treated for 30 minutes at 80-90 and liquor ratio 40:1 in an aqueous bath set with grams per litre of the brightening agent described in Example 6., with subsequent rinsing and drying. The fabric displays a pronounced, clear white effect which is very fast to light and chlorite.

What is claimed is:

1. A compound of formula material before processing. The films have a superior appearance to comparative films containing no brightener additive.

Application Example H 0.01 Part of the compound of formula I e is intimately mixed with 100 parts of polyethylene terephthalate granules for injection moulding. The mouldings'of this material are of superior appearance to mouldings without a brightener additive.

Application Example I in which R is sulpho, sulphonic amide, carboxylic amide or cyano,

R is hydrogen, chlorine, alkyl of 1 to 4 carbon atoms, carboxylic amide or cyano,

R is hydrogen, chlorine, methyl, hydroxymethyl,

chlo'romethyl or acetoxymethyl,

R is hydrogen, chlorine or methyl,

n is 0 or a whole number, and either T is hydrogen, chlorine, phenyl, alkyl of l to 8 carbon atoms, alkoxy of l to 4 carbon atoms, or cyano and T signifies hydrogen, or T and R both signify cyano.

2. A compound according to claim 1 wherein, where T signifies an alkyl radical, such alkyl radical is of 1 to 4 carbon atoms.

3. A compound of claim 2, wherein T is hydrogen or a C alkyl radical and T is hydrogen.

4. A compound according to claim 1 wherein n is 0 or 1 to 3.

5. A compound of claim 3 and of formula which show good fastness to light, peroxide and chlorite.

Application Example K Unbleached cotton yarn is treated for 1 hour at 85-95 and liquor ratio 20:1 in an aqueous bath containing, per litre, 0.08 grams of one of the brightening agents specified in Example 6 or 29 to 41 and 2 grams of sodium chlorite, with subsequent rinsing and drying. A brilliant white effect of very good fastness is obtained on the yarn.

where or 1 to 3.

7. The compound of claim 6 which is of formula 8. The compound of claim 7 which is of formula 

1. A COMPOUND OF FORMULA
 2. A compound according to claim 1 wherein, where T1 signifies an alkyl radical, such alkyl radical is of 1 to 4 carbon atoms.
 3. A compound of claim 2, wherein T1 is hydrogen or a C1-4 alkyl radical and T2 is hydrogen.
 4. A compound according to claim 1 wherein n is 0 or 1 to
 3. 5. A compound of claim 3 and of formula
 6. A compound according to claim 5 wherein n is 0 or 1 to
 3. 7. The compound of claim 6 which is of formula
 8. The compound of claim 7 which is of formula 